HemoCD as an Artificial Oxygen Carrier: Oxygen Binding and Autoxidation

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<jats:title>Abstract</jats:title><jats:p>Despite many attempts to construct completely artificial systems for carrying oxygen (O<jats:sub>2</jats:sub>) in aqueous solution, no successful example had been reported until quite recently except for picket fence porphinatoiron(II) embedded in liposomal membrane. We newly prepared a 1:1 complex (hemoCD) of 5,10,15,20‐tetrakis(4‐sulfonatophenyl)porphinatoiron(II) (Fe[II]TPPS) and a per‐<jats:italic>O</jats:italic>‐methylated β‐cyclodextrin dimer having a pyridine linker (Py3CD). HemoCD binds O<jats:sub>2</jats:sub> reversibly in aqueous solution. The oxygen affinity <jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/AOR_704_mu1.gif" xlink:title="inline image" /> corresponding to the partial O<jats:sub>2</jats:sub> pressure, at which half of the hemoCD molecules are oxygenated, was 16.9 torr in phosphate buffer at pH 7.0 and 25°C. Oxy‐hemoCD was gradually autoxidized (<jats:italic>t</jats:italic><jats:sub>1/2</jats:sub> = 30.1 h) due to nucleophilic attack of a water molecule to the O<jats:sub>2</jats:sub>–Fe bond. Encapsulation of the iron center of Fe(II)TPPS by two cyclodextrin truncated cones is essential for binding of O<jats:sub>2</jats:sub> to the ferrous center of the porphyrin. This manuscript reports the basic characteristics of hemoCD and the possible future utility of a totally artificial O<jats:sub>2</jats:sub> carrier.</jats:p>

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